US6936235B2 - Process for preparation of zirconium tungstate ceramic body, zirconium tungstate ceramic body prepared thereby, and temperature compensated fiber bragg grating device - Google Patents
Process for preparation of zirconium tungstate ceramic body, zirconium tungstate ceramic body prepared thereby, and temperature compensated fiber bragg grating device Download PDFInfo
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- US6936235B2 US6936235B2 US10/041,325 US4132502A US6936235B2 US 6936235 B2 US6936235 B2 US 6936235B2 US 4132502 A US4132502 A US 4132502A US 6936235 B2 US6936235 B2 US 6936235B2
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- G02B6/02057—Optical fibres with cladding with or without a coating comprising gratings
- G02B6/02076—Refractive index modulation gratings, e.g. Bragg gratings
- G02B6/02171—Refractive index modulation gratings, e.g. Bragg gratings characterised by means for compensating environmentally induced changes
- G02B6/02176—Refractive index modulation gratings, e.g. Bragg gratings characterised by means for compensating environmentally induced changes due to temperature fluctuations
- G02B6/0218—Refractive index modulation gratings, e.g. Bragg gratings characterised by means for compensating environmentally induced changes due to temperature fluctuations using mounting means, e.g. by using a combination of materials having different thermal expansion coefficients
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Definitions
- the present invention relates to the preparation of zirconium tungstate (ZrW 2 O 8 ) ceramic body, a modified zirconium tungstate ceramic body, and the use of the modified zirconium tungstate ceramic body to provide a temperature compensated optical fiber bragg grating (FBG) device.
- ZrW 2 O 8 zirconium tungstate
- FBG temperature compensated optical fiber bragg grating
- Optical fiber bragg grating is commonly applied in various components for manufacturing dense wavelength division multiplexing (DWDM), such as FBG stabilizing laser source, and various DWDM devices used in multiplexer, de-multiplexer, and optical add-drop multiplexer (OADM).
- DWDM dense wavelength division multiplexing
- OADM optical add-drop multiplexer
- increment of environmental temperature may affect the performance of the FBG. Because the grating space and index of refraction of the FBG determine the central frequency of the reflected light, special care must be given to ensure the precision of the FBG. Since increment of environmental temperature will change the index of refraction of the FBG, thereby causing increment of the wavelength of the optical fiber thereby deviating from the designated central wavelength, measures shall be taken to prevent occurrences of such changes.
- U.S. Pat. No. 5,042,898 discloses a temperature compensated FBG device.
- the device comprises two metals with different thermal expansion coefficients.
- Relevant references further include, such as U.S. Pat. No. 5,703,978 and Applied Optics. , Vol. 34 (30), p.6859, 1995 (G. W. Yoffe et. al.).
- the prior art still has the drawbacks of uneasily attaining the desired precision, being complicated in structures, involving difficult preparation steps, and being higher in cost. Therefore, it would be highly desirable to have an easily fabricated and simple temperature compensated FBG device with excellent temperature compensated result.
- the use of materials with negative coefficient of thermal expansion is one of the approaches and has been disclosed in U.S. Pat. No. 5,694,503, which is incorporated herein for reference.
- Zirconium tungstate is a known isotropic negative expansion material within a temperature range from 0.3 K to its decomposition temperature of about 1050 K. This material was first synthesized by J. Graham et al. (J. Am. Ceram. Soc., 42 [11] 570, 1959) in 1959 and its negative expansion property was discovered in 1968 (J. Am. Ceram. Soc., 51 [4] 227, 1968).
- ZrW 2 O 8 is formed from ZrO 2 and WO 3 at 1105° C., and melts at 1257° C.; apparently it is only thermodynamically stable within a temperature range of about 150° C. It must be quenched (rapidly cooled) from high temperature to avoid decomposition into ZrO 2 and WO 3 . Once formed, nevertheless, ZrW 2 O 8 has a high degree kinetic stability, in metastable condition, below 770° C. (1050 K). Thus, ZrW 2 O 8 will decompose into ZrO 2 and WO 3 when heated to about 770° C., and react to reform ZrW 2 O 8 if the temperature is increased to 1105° C.
- the preparation of ceramic body includes forming ceramic powders by the solid-state reaction or chemical synthesis process, grinding the powders, and compaction the grinded powders and sintering. Specifically, the preparation of single phase ceramic powders is followed by the sintering densification of the powders.
- the zirconium tungstate ceramic body is normally prepared by using the above solid-state reaction process or chemical synthesis process.
- the ceramic powders were prepared by solid-state reaction, and then sintered to provide zirconium tungstate ceramic bodies.
- zirconium tungstate ceramic bodies For example, according to the process described in Solid State Comm. , 114, 453, 2000 (Yamamura et al.), weighted with appropriate ratio and mixed ZrO 2 and WO 3 powders were compacted and then calcined at 1473K for 12 hours in air to carry out the solid-state reaction to form zirconium tungstate, which was then rapidly cooled down to room temperature. After grinding the pellets, the resulting powders were compacted again and then sintered at 1473K for 12 hours for densification and quenched in liquid nitrogen to form a single-phase zirconium tungstate ceramic body.
- the solid-state sintering process for the preparation of zirconium tungstate ceramic bodies normally requires ten or more hours to provide a pure phase zirconium tungstate ceramic bodies. Furthermore, if the particle sizes of the raw material powders are inappropriate or the admixing is unwell, it is difficult to obtain a uniform and single phase zirconium tungstate ceramic body by solid-state reaction process. The applicability of the zirconium tungstate ceramic body prepared thereby will thus be affected.
- the precipitate is heated to provide a mixture comprising ZrO 2 and WO 3 or ZrW 2 O 8 .
- the mixture is then grinded and re-heated to obtain a single-phase zirconium tungstate. It has been proved that the chemical synthesis process provides an efficient method to control the particle sizes of powders and the admixing.
- the process needs a solvent to adjust the pH value of the solution to obtain the precipitate of Zr 4+ and W 6+ and also requires another step of heating the precipitate.
- the preparation time is long and the preparation steps are complicated.
- the inventors of the present invention has found that when preparing zirconium tungstate by the reactive sintering process, the addition of powders of zirconium tungstate single crystal in the powders of raw materials comprising the Zr-containing compound and W-containing compound as the seeds for the formation of the grain of zirconium tungstate can reduce the formation energy and effectively simplify the procedure, shorten preparation time and save cost while obtaining zirconium tungstate ceramic bodies with uniform microstructure.
- the present invention efficiently provides the ceramic body with a desired expansion coefficient to provide the desired temperature compensation effect on FBG.
- the present invention relates to a process for the preparation of zirconium tungstate ceramic body, comprising
- the chemical reaction of the raw materials powders and the sintering densification of the compact are carried out in one heating treatment step, i.e., accomplishing the production of zirconium tungstate and the sintering densification of the compact in the same heating treatment step, to provide the desired zirconium tungstate ceramic body.
- the process of the present invention can effectively simplify the procedure, shorten preparation time, save the cost, and provide the zirconium tungstate ceramic body with uniform microstructure.
- the process of the present invention can further tune the thermal expansion coefficient of a zirconium tungstate ceramic body.
- a second phase of residual ZrO 2 or WO 3 is formed inside the zirconium tungstate ceramic body to tune the thermal expansion coefficient as desired.
- a second phase or pores uniformly distributed inside the zirconium tungstate ceramic body can be formed to make the thermal expansion coefficient changed.
- the present invention further relates to a temperature compensated FBG device, which comprises a substrate made of the zirconium tungstate ceramic body of the present invention.
- the device can further have an adhesive layer with positive thermal expansion coefficient on the substrate, or be further fitted with a low thermal expansion coefficient material between the optical fiber and the substrate of zirconium tungstate, or be further fitted with a tuning means to attain the purpose of controlling the center wavelength of FBG.
- FIG. 1 is a top view of a temperature compensated FBG device comprising a zirconium tungstate ceramic substrate according to the present invention, wherein the device further comprises an adhesive layer with positive thermal expansion coefficient;
- FIG. 2 is a top view of another temperature compensated FBG device comprising a zirconium tungstate ceramic substrate according to the present invention, wherein the device further comprises a low thermal expansion coefficient material;
- FIG. 3 is a cross-sectional view of another temperature compensated FBG device comprising a zirconium tungstate ceramic substrate according to the present invention, wherein the compensated device further comprises a tuning device; and
- FIG. 4 shows the curves illustrating the relative expansion of the zirconium tungstate ceramic bodies of Examples 1 to 5 over temperature.
- the present invention provides a process for the preparation of zirconium tungstate ceramic body, comprising
- the Zr-containing compound and W-containing compound can be any Zr-containing compounds and W-containing compounds suitable to the reactive sintering process.
- the compounds can be the oxides, sulfates, carbonates, nitrates, acetates, sulfides, or hydroxides, of Zr and W, tungsten metal, or tungstic acid (H 2 WO 4 ) or mixture thereof, the oxides of Zr and W, i.e., ZrO 2 and WO 3 , are preferred.
- the temperature for reactive sintering the compacts is typically from about 1105° C. to about 1257° C., preferably, about 1150° C. to about 1200° C. and the reactive sintering duration is typically from about 1 to about 10 hours, preferably, about 3 to about 8 hours, and more preferably, about 4 to about 6 hours. Generally, as the sintering temperature is higher, the required sintering duration will be shorter.
- the binder for the process of the present invention is selected from conventional organic binders, e.g., the binders disclosed in U.S. Pat. No. 5,694,503.
- the specie and amount of the binder are not critical to the process of the present invention.
- Persons skilled in the art can select the proper species and amount of the binder as required to practice the process of the present invention.
- the ZrW 2 O 8 seeds inside the green body may decompose into ZrO 2 and WO 3 when heated to 770° C., the ZrO 2 and WO 3 in situ react to form ZrW 2 O 8 when continuously heated at higher temperature.
- This reaction of in situ forming ZrW 2 O 8 is earlier than the reaction of powders of raw materials, thus the in situ formed ZrW 2 O 8 still can be the seeds of the reaction to improve the uniformity of the ceramic body.
- the thermal expansion coefficient of the ceramic substrate As to demands for FBG package, it is necessary to tune the thermal expansion coefficient of the ceramic substrate.
- the purpose of tuning the thermal expansion coefficient can be achieved by fabricating a composite or porous ceramic body.
- the present invention further provides a modified zirconium tungstate ceramic body with an tuned thermal expansion coefficient, by controlling the ratio of the raw material reactants in the entire reaction system, or by controlling the species and amount of the incorporated additives to form a second phase or pores uniformly distributed in the sintered zirconium tungstate ceramic body.
- the approach of controlling the ratio of Zr to W in the raw materials comprising the Zr-containing compound and W-containing compound lies in forming the second phase of residual ZrO 2 or WO 3 inside the sintered zirconium tungstate ceramic body, to prevent the added oxides different from the Zr-containing and W-containing compounds from reacting with the raw material reactants and the followed influence on the formation of zirconium tungstate. Also, the approach can prevent the formation of microcracks in the zirconium tungstate ceramic body because of the stress inside the materials upon the variation of temperature, raised from the nonuniform distribution or overly large particle size.
- the addition of inorganic binder in the raw materials powders can form a uniform distributed second phase grains inside the zirconium tungstate ceramic body after a high temperature treatment. Nevertheless, it should be noted that the formed oxides would not have influence on the reaction system of ZrO 2 and WO 3 .
- the inorganic binder can be Na 2 O.nSiO 2 that forms a second phase of residual Na 2 O, ZrSiO 4 , and minor amount of WO 3 after a heat treatment to achieve the purpose of tuning the thermal expansion coefficient as desired.
- the amounts of the residual ZrO 2 or WO 3 and/or inorganic binder can be determined by any of known calculation models, such as that disclosed in U.S. Pat. No. 5,694,503. The amounts are not the technical characteristics of the present invention.
- the thermal expansion coefficient can be tuned by forming porous ceramic bodies.
- porous ceramic bodies There are many processes for the preparation of porous ceramic bodies, generally by adding an organic binder that can generate pores inside the zirconium tungstate ceramic bodies after sintering.
- the thermal expansion coefficient of zirconium tungstate ceramic can be tuned as desired by adding an organic binder to the raw materials powders to form a second phase of pores uniformly distributed inside the zirconium tungstate ceramic body after sintering.
- a direct-consolidation process as disclosed in J. European Ceramic Soc., 18, 131,1998 is preferred.
- the direct-consolidation process comprises admixing ceramic powders, an organic binder, and water under room temperature to form slurry, pouring the slurry into a mold and heating to the temperature above the gelation temperature of the binder to cure, then drying the cured product to obtain a ceramic green body. Then the ceramic green body is heated to remove the organic binder and sintered to obtain a porous ceramic body.
- the organic binder is preferably selected from the group consisting of starch and methylcellulose.
- the modified zirconium tungstate ceramic body with tuned thermal expansion coefficient can also be prepared by directly using powders of zirconium tungstate to replace the stoichiometric Zr-containing compound and W-containing compound, and by admixing the zirconium tungstate powders with the second phase forming-additive(s) followed by the sintering densification.
- the modified zirconium tungstate ceramic body according to the present invention is composed of zirconium tungstate matrix as the first phase and residues as the second phase, wherein the second phase is composed of the component(s) selected from the group consisting of ZrO 2 , WO 3 , Na 2 O+ZrSiO 4 , pores, and combination thereof.
- the present invention further relates to a temperature compensated FBG device comprising a substrate made of the modified zirconium tungstate ceramic body of the present invention.
- the device is now illustrated by the following embodiments.
- FIG. 1 is a temperature compensated optical fiber bragg grating device 10 , comprising a zirconium tungstate ceramic substrate 11 of the present invention, an adhesive layer 12 with positive thermal expansion coefficient coated on the substrate 11 (in this embodiment, the adhesive is coated on both side surfaces of the substrate), an optical fiber 13 affixed to the two ends of the substrate 11 by the affixed points of epoxide adhesive 15 , wherein the optical fiber 13 is embedded with gratings at the mid-section thereof to form a fiber bragg grating 14 .
- the thermal expansion coefficient of the compensated device can be further tuned to the desired value.
- FIG. 2 is another temperature compensated optical fiber bragg grating device 20 , comprising a zirconium tungstate ceramic substrate 21 of the present invention and a low expansion coefficient material 26 .
- an optical fiber 23 is affixed to the two ends of the substrate 21 by the affixed points of epoxide adhesive 25 .
- the optical fiber 23 is embedded with gratings at the mid-section thereof to form a fiber bragg grating 24 .
- the low expansion coefficient material 26 is set between the substrate 21 and the optical fiber 23 .
- the low expansion coefficient material 26 is directed to the one with a thermal expansion coefficient lower than that of stainless steel, preferably, lower than one tenth of stainless steam or less, and can be selected from quartz, invar, etc.
- the central wavelength of fiber bragg grating 24 can be further tuned according to the demand for specification.
- FIG. 3 is another temperature compensated optical fiber bragg grating device 30 , comprising a zirconium tungstate ceramic substrate 21 of the present invention and a threaded rod 37 of a manual adjusting device.
- the substrate 31 is formed with an indenting 38 and two arms 301 and 302 thereon.
- the threaded rod 37 having a positive screw thread 371 and a counter screw thread 372 is disposed across the indenting 38 along the longitudinal direction of the substrate 31 , wherein the positive screw thread 371 and counter screw thread 372 engage the arms 301 and 302 , respectively.
- the optical fiber 33 is embedded with gratings at the mid-section thereof to form a fiber bragg grating 34 .
- the threaded rod 37 drives the arm 301 gradually closer to the arm 302 .
- the threaded rod 37 drives the arm 302 gradually away from the arm 301 . Since the optical fiber 33 having the fiber bragg grating 34 is affixed to the arms 301 and 302 , the threaded rod 37 can manually control the length of the fiber bragg grating to adjust its central wavelength.
- the ZrO 2 and WO 3 powders in the molar ratio of 1:2 (Zr:W) and an organic binder were dispersed in deionized water, grounded and admixed to form a slurry.
- the mixed well slurry was dried at 105° C.
- the dried powders of 25 g were dry-pressed to form a plate-shaped compact of 60 mm ⁇ 35 mm.
- the plated-shaped compact was sintered at 1200° C. for 6 hours and then was immediately quenched to room temperature in the air to obtain a single-phase ⁇ -ZrW 2 O 8 ceramic body.
- the thermal expansion coefficient of the zirconium tungstate ceramic body measured by dilatometer over ⁇ 40° C.
- zirconium tungstate powders were added to the mixture of ZrO 2 and WO 3 powders in the molar ratio of 1:2 (Zr:W) as the seeds for the formation of zirconium tungstate grain by reactive sintering, the raw materials were then ground and admixed in deionized water. The well mixture was admixed with an organic binder and then dried. The dried powders of raw materials of 25 g were dry-pressed to form a plate-shaped compact of 60 mm ⁇ 35 mm. The plate-shaped compact was sintered at 1150° C. for 4 hours and then was immediately quenched to room temperature in the air to obtain a single-phase ⁇ -ZrW 2 O 8 ceramic body.
- the sintering temperature and duration were obviously lessened.
- the thermal expansion coefficient of the zirconium tungstate ceramic body was ⁇ 10.85 ⁇ 10 ⁇ 6 K ⁇ 1 .
- the relative expansion of the zirconium tungstate ceramic body over temperature was shown as curve e in FIG. 4 .
- the zirconium tungstate ceramic substrate was diced by a diamond saw to a desired size and then packaged.
- Example 1 After 10.4 g of ZrO 2 powders and 31.6 g of WO 3 powders were ground and admixed in deionized water, an organic binder was added to form slurry and then dried at 105° C. The preparation and processing after drying were those as shown in Example 1.
- the thermal expansion coefficient of the obtained zirconium tungstate ceramic body was ⁇ 9.51 ⁇ 10 ⁇ 6 K ⁇ 1 .
- the relative expansion of the zirconium tungstate ceramic body over temperature was shown as curve c in FIG. 4 .
- the raw materials were replaced with 10.316 g of ZrO 2 powders, 31.284 g of WO 3 powders, and 0.4 g of ZrW 2 O 8 powders.
- the subsequent admixing steps were the same as the above. Because adding the seeds, the obtained plate-shaped compact could form zirconium tungstate ceramic body by the reactive sintering at 1150° C. for 4 hours. The sintering temperature and sintering duration were obviously lessened. The property of the obtained ceramic body was identical to the above one.
- the relative expension of the zirconium tungstate ceramic body over temperature was shown as curve a in FIG. 4 .
- the zirconium tungstate ceramic substrate was diced by a diamond saw to a desired size and then packaged.
- the relative expansion of the zirconium tungstate ceramic body over temperature was shown as curve b in FIG. 4 .
- the zirconium tungstate ceramic substrate was diced by a diamond saw to a desired size and then packaged.
- the raw materials were replaced with 8.316 g of ZrO 2 powders, 31.284 g of WO 3 powders, and 0.4 g of ZrW 2 O 8 powders.
- the subsequent admixing steps were the same as the above. Because adding the seeds, the obtained green body could form porous zirconium tungstate ceramic body by the reactive sintering at 1160° C. for 3.5 hours. The sintering temperature and sintering duration were obviously lessened. The property of the obtained ceramic body was identical to the one above.
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Abstract
Description
- (a) dispersing the raw materials powders comprising a Zr-containing compound and a W-containing compound and powders of zirconium tungstate single crystal in deionized water and through grinding and well admixing to form a slurry;
- (b) adding a binder to the slurry of (a) to form a mixture;
- (c) drying the mixture of (b) to obtain granules and then dry-pressing them to form a compact; and
- (d) sintering the compact to obtain the zirconium tungstate ceramic body.
- 10, 20, or 30 represents a temperature compensated FBG device;
- 11 represents a zirconium tungstate ceramic substrate;
- 12 represents an adhesive layer;
- 13 represents an optical fiber;
- 14 represents a fiber bragg grating;
- 15 represents an affixing point of epoxide adhesive;
- 21 represents a zirconium tungstate ceramic substrate;
- 23 represents an optical fiber;
- 24 represents a fiber bragg grating;
- 25 represents an affixing point of epoxide adhesive;
- 26 represents a low thermal expansion coefficient material;
- 301 or 302 represents an arm;
- 31 represents a zirconium tungstate ceramic substrate;
- 33 represents an optical fiber;
- 34 represents a fiber bragg grating;
- 35 represents an affixing point of epoxide adhesive;
- 37 represents a counter threaded rod;
- 371 represents a positive screw thread;
- 372 represents a counter screw thread; and
- 38 represents an indenting.
- (a) dispersing the raw materials powders comprising a Zr-containing compound and a W-containing compound and powders of zirconium tungstate single crystal in deionized water and through grinding and well admixing to form a slurry;
- (b) adding a binder to the slurry of (a) to form a mixture;
- (c) drying the mixture of (b) to obtain granules and then dry-pressing them to form a compact; and
- (d) sintering the compact to obtain the zirconium tungstate ceramic body.
Claims (26)
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TW90120128 | 2001-08-16 | ||
TW090120128A TWI234554B (en) | 2001-08-16 | 2001-08-16 | Process for preparation of zirconium tungstate ceramic body, zirconium tungstate ceramic body prepared thereby, and fiber bragg grating temperature compensated device |
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US6936235B2 true US6936235B2 (en) | 2005-08-30 |
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Cited By (4)
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AT502394B1 (en) * | 2005-09-07 | 2007-03-15 | Arc Seibersdorf Res Gmbh | METHOD FOR PRODUCING A CERAMIC MATERIAL AND CERAMIC MATERIAL |
US20090278580A1 (en) * | 2008-05-09 | 2009-11-12 | Kim Kwan Dong | Clock control circuit and a semiconductor memory apparatus having the same |
CN103529552A (en) * | 2013-09-22 | 2014-01-22 | 北京石油化工学院 | LD (Laser Diode) laser phase mixing device and method |
RU2639244C1 (en) * | 2016-11-25 | 2017-12-20 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" (ТГУ) | Method of producing zirconium tungstate powder |
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Also Published As
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TWI234554B (en) | 2005-06-21 |
US20030054941A1 (en) | 2003-03-20 |
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